CN103073569B - Production process of organosilane polysulfide - Google Patents
Production process of organosilane polysulfide Download PDFInfo
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Abstract
The invention discloses a production process of organosilane polysulfide. The production process comprises the following steps of: 1, adding elemental sulfur in sodium hydroxide at a temperature of 90-100 DEG C by batches according to the calculation proportion, controlling the reaction temperature and keeping for a period of time to form polysulfide Na2Sn, wherein n has the meaning described in the specification; 2, enabling the polysulfide obtained in the step 1 to condensate with an organosilane compound in the following formula (2) under the existence of a phase transfer catalyst and a hydrolysis buffer agent to obtain a sulfur-containing silane crude product (RO)3-mRmSi-Alk-X(2), wherein X is chlorine, bromine and iodine, and R, Alk and m have the meanings described in the specification; 3, separating a water phase from an organic phase; 4, enabling the organic phase to be in contact with ion change resin for carrying out decoloring and desalting; and 5, distilling, cooling and filtering to obtain an organosilane polysulfide finished product.
Description
Technical field
The present invention relates to a kind of production technique of organosilane polysulfide of environmental protection.
Background technology
Sulfur-containing organosilicon alkane coupling agent has been widely used in each industrial circle.Especially in rubber industry, add the performance that silane coupling agent can significantly strengthen white carbon black, improve the tensile strength of cross-linked rubber and the thermal-oxidative aging property of sizing material.Especially, two-[γ-(triethoxysilicane) propyl group] tetrasulfide (HP-669) has multi-function action to rubber, can be used as senior vulcanizing agent, activator, strengthening agent, tenderizer and flexibilizing agent in rubber industry, can improve micelle tensile strength, wear resistance, fatigue resistance and elasticity, process rubber and filler with it, make the gained sizing material reach delayed coking, accelerated cure and raising reinforcing effect.
Traditional two-[γ-(triethoxysilicane) propyl group]-tetrasulfide can prepare by several different methods.A kind of method is to make alkali metal alcoholate and hydrogen sulfide reaction generate alkali metal hydrosulfide, then obtains alkali metalsulphide with the basic metal reaction.Make again gained alkali metalsulphide and reaction of Salmon-Saxl obtain alkali metals polysulfide, then with γ-chloropropyl triethoxysilane reaction.Also can in the situation of not using hydrogen sulfide, prepare polysulfide, metal alkoxide is reacted with elemental sulfur in alcohol, or make sodium Metal 99.5 and elemental sulfur and alcohol reaction, react with chloropropyl triethoxysilane again.
Another kind method is not have to make sulphur, basic metal and the reaction of alkyl halide TMOS in the situation of solvent or in the presence of aprotic solvent.
The third method is Sodium sulphate anhydrous, 99min or Sodium sulfhydrate and sulphur to be reacted generate sodium polysulphide in dehydrated alcohol, then reacts with chloropropyl triethoxysilane.
The 4th kind of method is to make sodium hydroxide and the synthetic sodium polysulphide of elemental sulfur reaction in saturated sodium-chloride water solution, then reacts with chloropropyl triethoxysilane.
Wherein prepare sodium polysulphide with sodium sulphite or Sodium sulfhydrate and have at least following side reaction:
① Na
2S + S → Na
2S
2
② Na
2S + 2S → Na
2S
3
③ Na
2S + 4S → Na
2S
5
④ Na
2S + 5S → Na
2S
6
⑤ Na
2S + 6S → Na
2S
7
⑥ Na
2S + 7S → Na
2S
8
In actual production process, above-mentioned reaction does not occur successively, but occurs simultaneously, so polysulfide often is the mixture of multiple polysulfide, wherein Na in the products therefrom
2S
nN be the mean value of sulphur chain length.Because uncontrollable these side reactions of prior art, prepared polysulfide sulphur chain length n is all less than 4, and most less than 3, wherein the content of tetrasulfide is low.Wherein side reaction 1. and existence 2. make in the product sulphur content on the low side, the existence that 3.-6. side reaction waits makes product color and outward appearance not good, easily produces precipitation.
Use hydrogen sulfide or Sodium sulfhydrate to cause producing a large amount of hydrogen sulfide tail gas, serious environment pollution.And prior art is not instructed the method that absorbs and process tail gas.
Prior art is used sodium hydroxide directly and the elemental sulfur reaction still can not be avoided the problems referred to above, and mean value n great majority are all less than 4, and the content of tetrasulfide is on the low side, and the content of S5-S6 is higher, has affected quality product.
In addition, also there is multiple other shortcoming in aforesaid method: the price of used sodium Metal 99.5 and sodium ethylate is all very expensive, and there is larger potential safety hazard in sodium Metal 99.5 in storage process; With an organic solvent mediating, is not eco-friendly, and its recovery makes production cost very high, when particularly using ethanol, because its flash-point is low, has very large potential safety hazard; Raw material and product are met the water facile hydrolysis, must guarantee to react under anhydrous state, and be difficult to obtain and keep required anhydrous condition on the technical scale; Need nitrogen protection in the reaction process, strict to operational requirement, processing condition are wayward, increased simultaneously production cost.In addition, the sodium sulphite used of reaction and Sodium sulfhydrate be very easy to make moist, oxidation and spontaneous combustion, be difficult for storing, and the sodium sulphite after making moist and Sodium sulfhydrate all exist with the form that contains crystal water usually, this crystal water is difficult to remove, and uses the sulfide with crystal water to cause easily the product hydrolysis to be lost efficacy as raw material.
A lot of teach literatures for the production of the phase transfer catalytic technology of sulfur-containing organosilicon hydride compounds, overcome to a certain extent some practical problemss relevant with the production method of above-mentioned sulfur-containing organosilicon alkane coupling agent.But adopt phase transfer of technology still to have many practical problemss in technical scale, for example, in the preparation of sulfur-containing organosilicon alkane, need to control the reactivity of phase-transfer catalyst, reaction can effectively and safely be carried out on technical scale.When in phase transfer catalytic technology, making raw material with the sulfhydrate of basic metal or ammonium, produce dangerous in the side reaction and the hydrogen sulfide of flavor is arranged, also have a strong impact on its quality product even contain the hydrogen sulfide of trace in the final product.Another related problem of employing phase transfer catalytic technology is that the alkoxyl group on organic silane compound or the initial silane reaction thing is caused gelling by the hydrolysis of water react thing.In addition, the phase transfer catalysis process of prior art produces and contains a large amount of unreacted S-contained substances, may precipitate in stored prod, causes the sulfide distribution of product to change, and therefore also needs to improve stability, outward appearance and the purity of the finished product.Prior art decolouring is processed and is all adopted gac, and it exists the discoloring agent consumption large, and decolorizing effect is undesirable, the finished product poor storage stability, and the defective such as darken after 3-6 month.
Summary of the invention
The invention provides improving one's methods of a kind of organosilane polysulfide based on phase transfer catalytic technology production formula (1),
(RO)
3-mR
mSi-Alk-S
n-Alk-SiR
m(OR)
3-m （1）
Wherein:
Each R is the monovalence alkyl that contains 1 to 6 carbon atom independently, preferable methyl, ethyl, propyl group or normal-butyl;
Alk is the bivalent hydrocarbon radical that contains 1 to 12 carbon atom independently, and is preferred-(CH
2)
x-, wherein x is selected from 1,2,3,4,5,6;
M is 0 to 2 integer, and preferred m is 0;
N is the number between 2 to 5, preferably 3.5≤n≤4.5, more preferably 3.5≤n≤4.2, more preferably 3.6≤n≤4.0, most preferably n=3.75.
Said method comprising the steps of:
(1) add elemental sulfur in the calculating ratio in sodium hydroxide under 90-100 ℃ temperature, the control temperature of reaction also keeps certain hour in batches, to form sodium polysulphide Na
2S
n, wherein n has aforesaid implication;
(2) organic silane compound that makes step (1) gained sodium polysulphide and following formula (2) condensation in the presence of phase-transfer catalyst and hydrolysis buffer reagent obtains the sulfuric silane crude product
(RO)
3-mR
mSi-Alk-X （2）
Wherein, X is chlorine, bromine or iodine, is preferably chlorine, and R, Alk, m have aforesaid implication;
(3) water phase separated and organic phase;
(4) make organic phase contact the desalination of decolouring with ion exchange resin;
(5) distillation, cold filtration obtains finished product.
In one embodiment of the invention, the organosilane polysulfide of formula (1) is
(C
2H
5O)
3Si-(CH
2)
3-S
n-(CH
2)
3-Si(OC
2H
5)
3 （1'）
Wherein: 3.5≤n≤4.2, preferably 3.6≤n≤4.0, more preferably n=3.75;
The organic silane compound of formula (2) is
(C
2H
5O)
3Si-(CH
2)
3-Cl （2'）。
In one embodiment of the invention, described method comprises alternatively: (6) use the sodium hydroxide absorption tail gas.
Preferably, the described absorption tail gas step of step (6) comprises: make tail gas successively by comprising Multi-stage spiral-plate tower and the packing tower of liquid caustic soda.
In one embodiment of the invention, the ratio of sodium hydroxide and sulphur is 1:1～1:2 in the step (1), is preferably 3:5.
In another embodiment of the invention, the temperature of reaction of step (1) is 96～100 ℃, preferred 98 ℃.
In another embodiment of the invention, after finishing, the reaction of step (1) directly enters step (2) without separating.
In one embodiment of the invention, the described phase-transfer catalyst of step (2) is quaternary ammonium salt-type phase transfer catalyst.
Described quaternary ammonium salt preferably is selected from one or more in Tetrabutyl amonium bromide, tetrabutylammonium chloride, tetraethylammonium bromide, the etamon chloride.
In another embodiment of the invention, the described hydrolysis buffer reagent of step (2) is selected from one or more in sodium bicarbonate, saleratus, yellow soda ash, salt of wormwood, sodium bisulfite, the S-WAT.
In another embodiment of the invention, the pH value of step (2) control reaction system is in the scope of 8-12.Preferably control the pH value in the scope of 9-12, more preferably controlling the pH value is 10.
The inventor is surprisingly found out that, by adjusting the conditions such as ratio, addition sequence and temperature of reaction of sodium hydroxide and elemental sulfur, can effectively control each reaction and occur by needed degree, obtains to have the average sulfur chain length (n value) of expectation.For example, first sodium hydroxide is heated to temperature of reaction, then add elemental sulfur in the ratio of calculating in batches, the control temperature of reaction, the fully rear stopped reaction of question response, products obtained therefrom not only sulphur content is moderate, the content of the components such as pentasulfide, hexasulfide, heptasulfide, eight sulfide significantly descends, stability obviously improves, and storing after 1 year still is light yellow transparent liquid, produces without precipitation and floss.
As replacement scheme of the present invention, also can directly replace sodium hydroxide to react with sodium sulphite.Adjust ratio and the addition sequence of sodium sulphite and elemental sulfur according to method of the present invention and also can effectively control each reaction by needed degree generation, thereby improve the content of tetrasulfide in the product.
The condensation in the presence of phase-transfer catalyst and hydrolysis buffer reagent of the organic silane compound of polysulfide and formula (2), the existence of hydrolysis buffer reagent can be controlled at proper range with the pH of reaction system, but the on the one hand generation of establishment siloxanes and end product hydrolysis reaction, the generation of having stopped on the other hand hydrogen sulfide tail gas.
The present invention can effectively remove yin, yang ion variable color impurity and other foreign pigment owing to used ion exchange resin to carry out ion exchange reaction, and the discoloring agent consumption is little, finished product color and luster stable homogeneous, and storing still is light yellow after 1 year, produces without precipitation.
Description of drawings
Fig. 1: shown gained of the present invention two-the HPLC detected result of [γ-(triethoxysilicane) propyl group] each composition of polysulfide.
Embodiment
Following examples only are used for further explaining the present invention, rather than limit the scope of the invention.All apparent changes of the present invention or modification all fall into protection scope of the present invention.
Embodiment 1
(1) drop into the aqueous solution that 24 kg sodium hydroxide are made in sulfur melting kettle, be heated to 90～100 ℃, then 16 kg sulphur are dropped in the sulfur melting kettle, 90～100 ℃ of control temperature of reaction are incubated 1 hour, drop into 16kg sulphur again, are incubated 1～3 hour.Gained sodium polysulphide reaction solution is directly used in next step reaction without separation.
(2) (1) step gained sodium polysulphide reaction solution is pumped in the condensation reaction still, 80-82 ℃ of control temperature adds the aqueous solution of 4 kg Tetrabutyl amonium bromides as phase-transfer catalyst, adds 5% sodium hydrogen carbonate solution as the hydrolysis buffer reagent, makes pH value 9-10.Add 96 kg γ-chloropropyl triethoxysilanes (γ 2) behind the 5min and carry out condensation reaction, 85 ± 2 ℃ of temperature of reaction, time 60min.Sampling detects the qualified rear stopped reaction of residual γ 2 content 0.8-1.5%.
(3) after the crude product cooling, then separated salt water layer and organic layer carry out organic layer settlement separately, get the HP-669 crude product.
(4) the HP-669 crude product is dropped into the decolouring still, add the strongly acidic cation-exchange of handling well in advance, decoloured 2 hours.Filter.
(5) filtrate is through underpressure distillation, and cold filtration obtains finished product HP-669.Yield 98.4%.
(6) tail gas is absorbed by Multi-stage spiral-plate tower and packing tower, liquid caustic soda is as the absorption liquid of Multi-stage spiral-plate tower and packing tower.The tail gas absorption liquid is mainly sodium sulphite, can continue and the synthetic sodium polysulfide solution of sulfur reaction.
Detect through the HPLC-GC method, sulphur content is among the finished product HP-669: 22.5 ± 1.5%; S2 content is: 17 ± 3%; S3 content is: 30 ± 4%; S4 content is: 24 ± 4%; S5-S8 content: 27 ± 3%; Average sulfur chain length n:3.75 ± 0.15.
Detect Yi Chun＜=0.5% through GC, generally be worth between 0.01-0.20.
Finished product is light yellow transparent liquid, and color and luster is even, and storing still is light yellow after 1 year, without precipitation and floss.
Comparative Examples 1
Add the aqueous solution that 32 kg sulphur and 24 kg sodium hydroxide are made in the sulfur melting kettle, then be heated to 90～100 ℃, be incubated 2～4 hours.All the other steps are with embodiment 1.
Detect through the HPLC-GC method, S2 content is that 3.4%, S3 content is that 18.4%, S4 content is that 34.2%, S5-S8 content is 42.3% among the finished product HP-669.
After storing 120 days, finished product HP-669 have precipitation and floss to form.
This shows that the present invention adopts the mode that in batches adds elemental sulfur, and control temperature of reaction, can significantly reduce the content of S5-S8, improve the stability of product, improve the quality of product.
Comparative Examples 2
Except not adding the hydrolysis buffer reagent, all the other steps are identical with embodiment 1 with reaction conditions.After testing, ethanol content is 0.5% in the finished product.
This shows that the present invention can obviously reduce hydrolysis degree by adding the hydrolysis buffer reagent, improves product yield.
Comparative Examples 3
Adopt the Zeo-karb in the gac alternative embodiment 1, all the other steps are identical with embodiment 1 with reaction conditions.Gained finished product HP-669 is yellow obfuscation, stores 3-6 and darkens after individual month, and have floss to produce.
It is a difficult problem using the synthetic HP-669 of phase transfer catalysis process that common activated carbon decolorizing can't effectively decolour, and the present invention can the various foreign pigments of effective elimination by ion exchange reaction, the stability of raising product.
The effect that the present invention obtains:
1. sulphur content is moderate in the product, and tetrasulfide content is high, can reach more than 50%.
2. ethanol can reach in 0.1% in the qualified rear crude product of condensation reaction, shows that hydrolysis degree is extremely low, and product yield is higher than 98%;
3. condensation reaction speed is fast, can finish reaction in 60 min, and efficient is high.
4. make spent ion exchange resin carry out ion exchange reaction, can remove positively charged ion variable color impurity, finished product still is light yellow after storing 1 year.
5. having realized that tail gas absorbs is combined with recycle, effectively reduces three wastes problem, has realized that phase transition synthesizes the environmental protection of 669 techniques.
Claims (17)
1. the production technique of an organosilane polysulfide, the organosilane polysulfide is following formula (1),
(RO)
3-mR
mSi-Alk-S
n-Alk-SiR
m(OR)
3-m （1）
Wherein:
Each R is the monovalence alkyl that contains 1 to 6 carbon atom independently,
Alk is the bivalent hydrocarbon radical that contains 1 to 12 carbon atom independently,
M is 0,
And 3.5≤n≤4.5,
Described production technique may further comprise the steps:
(1) add elemental sulfur in the calculating ratio in sodium hydroxide under 90-100 ℃ temperature, the control temperature of reaction also keeps certain hour in batches, to form sodium polysulphide Na
2S
n, wherein n has aforesaid implication;
(2) organic silane compound that makes step (1) gained sodium polysulphide and following formula (2) condensation in the presence of phase-transfer catalyst and hydrolysis buffer reagent obtains the sulfuric silane crude product
(RO)
3-mR
mSi-Alk-X （2）
Wherein, X is chlorine, bromine or iodine, and R, Alk, m have aforesaid implication;
(3) water phase separated and organic phase;
(4) make organic phase contact the desalination of decolouring with ion exchange resin;
(5) distillation, cold filtration obtains finished product.
2. production technique as claimed in claim 1 is characterized in that:
R is selected from methyl, ethyl, propyl group, normal-butyl;
Alk is-(CH
2)
x-, wherein x is selected from 1,2,3,4,5,6.
3. production technique as claimed in claim 1 is characterized in that:
The organosilane polysulfide of formula (1) is
(C
2H
5O)
3Si-(CH
2)
3-S
n-(CH
2)
3-Si(OC
2H
5)
3 （1'）
Wherein: 3.5≤n≤4.2
The organic silane compound of formula (2) is
(C
2H
5O)
3Si-(CH
2)
3-Cl （2'）。
4. production technique as claimed in claim 3 is characterized in that 3.6≤n≤4.0.
5. such as each described production technique of claim 1-4, characterized by further comprising following steps: (6) sodium hydroxide absorption tail gas.
6. production technique as claimed in claim 5, it is characterized in that: the described absorption tail gas step of step (6) comprises: make tail gas successively by comprising Multi-stage spiral-plate tower and the packing tower of liquid caustic soda.
7. such as each described production technique of claim 1-4, it is characterized in that: the ratio of sodium hydroxide and sulphur is 1:1～1:2 in the step (1).
8. production technique as claimed in claim 7 is characterized in that: the ratio of sodium hydroxide and sulphur is 3:5 in the step (1).
9. such as each described production technique of claim 1-4, it is characterized in that: the temperature of reaction of step (1) is 96～100 ℃.
10. production technique as claimed in claim 9, it is characterized in that: the temperature of reaction of step (1) is 98 ℃.
11. such as each described production technique of claim 1-4, it is characterized in that: directly enter step (2) without separating after the reaction of step (1) finishes.
12. such as each described production technique of claim 1-4, it is characterized in that: the described phase-transfer catalyst of step (2) is quaternary ammonium salt-type phase transfer catalyst.
13. production technique as claimed in claim 12, described quaternary ammonium salt is selected from one or more in Tetrabutyl amonium bromide, tetrabutylammonium chloride, tetraethylammonium bromide, the etamon chloride.
14. such as each described production technique of claim 1-4, it is characterized in that: the described hydrolysis buffer reagent of step (2) is selected from one or more in sodium bicarbonate, saleratus, yellow soda ash, salt of wormwood, sodium bisulfite, the S-WAT.
15. such as each described production technique of claim 1-4, it is characterized in that controlling the pH of step (2) in the scope of 8-12.
16. production technique as claimed in claim 15 is characterized in that controlling the pH of step (2) in the scope of 9-12.
17. production technique as claimed in claim 16, the pH value that it is characterized in that controlling step (2) is 10.
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| CN103788121B (en) * | 2014-01-28 | 2016-08-17 | 南京曙光硅烷化工有限公司 | The method producing light color polysulfide silanes coupling agent without buffer agent |
| CN105693576A (en) * | 2016-03-30 | 2016-06-22 | 洛阳和梦科技有限公司 | Preparation method of diallyl polythioether compounds |
| CN109180719A (en) * | 2018-09-03 | 2019-01-11 | 东营市金凤凰化工股份有限公司 | A kind of liquid alkaline prepares the technique and production system of silicon 69 |
| CN111518129B (en) * | 2020-05-22 | 2021-05-21 | 江西宏柏新材料股份有限公司 | Production system and production process for synthesizing sulfur-containing silane by continuous method |
| CN112358497B (en) * | 2020-11-19 | 2023-08-25 | 南京曙光新材料有限公司 | Preparation method of polysulfide silane coupling agent with lighter color |
| CN115286795A (en) * | 2022-08-31 | 2022-11-04 | 湖南西林环保材料有限公司 | Cyanuric sulfide high polymer material and preparation method and application thereof |
Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101092427A (en) * | 2007-07-25 | 2007-12-26 | 哈尔滨工业大学 | Method for preparing bi - [gamma - (triethoxy silicon) propyl tetrasulfide in aqueous phase |
| CN101768181A (en) * | 2010-01-28 | 2010-07-07 | 南京市化学工业研究设计院有限公司 | Method for preparing bis (triethoxypropylsilane) polysulfide |
-
2013
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Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101092427A (en) * | 2007-07-25 | 2007-12-26 | 哈尔滨工业大学 | Method for preparing bi - [gamma - (triethoxy silicon) propyl tetrasulfide in aqueous phase |
| CN101768181A (en) * | 2010-01-28 | 2010-07-07 | 南京市化学工业研究设计院有限公司 | Method for preparing bis (triethoxypropylsilane) polysulfide |
Non-Patent Citations (2)
| Title |
|---|
| 王叔清.由对硝基苯甲醚制备对氨基苯甲醚的工艺研究.《应用化工》.2003,第27页. |
| 由对硝基苯甲醚制备对氨基苯甲醚的工艺研究;王叔清;《应用化工》;20031231;第27页 * |
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Address after: 333311 Jiangxi province Leping City Tashan Industrial Park Industrial Road nine Patentee after: Jiangxi Acer Baixin materials Limited by Share Ltd Address before: 333300 Jiangxi city of Jingdezhen province Jingdezhen Leping City Industrial Road, Tashan Industrial Park No. nine Patentee before: Jingdezhen Hongbai Chemistry Technology Co., Ltd. |